See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/323233358

Chitosan/waste coffee-grounds composite: An efficient and eco-friendly

adsorbent for removal of pharmaceutical contaminants from water

Article  in  Carbohydrate Polymers · February 2018

DOI: 10.1016/j.carbpol.2018.02.018

CITATIONS READS

26 581

3 authors, including:

André R. Fajardo
Universidade Federal de Pelotas
78 PUBLICATIONS   2,180 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Development and Application of Materials Based on Biocompounds Isolated from Vegetal Biomass View project

Development of hybrid materials based on polymers for catalytic applications View project

All content following this page was uploaded by André R. Fajardo on 26 February 2018.

The user has requested enhancement of the downloaded file.

Accepted Manuscript

Title: Chitosan/waste coffee-grounds composite: An efficient

and eco-friendly adsorbent for removal of pharmaceutical
contaminants from water

Authors: Emanuele F. Lessa, Matheus L. Nunes, André R.

Fajardo

PII: S0144-8617(18)30156-5
DOI: https://doi.org/10.1016/j.carbpol.2018.02.018
Reference: CARP 13280

To appear in:

Received date: 5-12-2017

Revised date: 19-1-2018
Accepted date: 5-2-2018

Please cite this article as: Lessa, Emanuele F., Nunes, Matheus L., & Fajardo,
André R., Chitosan/waste coffee-grounds composite: An efficient and eco-friendly
adsorbent for removal of pharmaceutical contaminants from water.Carbohydrate
Polymers https://doi.org/10.1016/j.carbpol.2018.02.018

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
Chitosan/waste coffee-grounds composite: An efficient and eco-
friendly adsorbent for removal of pharmaceutical contaminants from
water

Emanuele F. Lessa, Matheus L. Nunes, André R. Fajardo*

Laboratório de Tecnologia e Desenvolvimento de Compósitos e Materiais Poliméricos (LaCoPol),

Centro de Ciências Químicas, Farmacêuticas e de Alimentos, Universidade Federal de Pelotas (UFPel),
Campus Capão do Leão s/n, 96010-900, Pelotas-RS, Brazil.

T
IP
(*)Corresponding author - E-mail: andre.fajardo@pq.cnpq.br - Phone: +55 53 3274-7356 - Fax: +55 53
3275-7354.

R
SC
U
N
A
M
ED

Highlights

>Composite films based on chitosan and waste coffee grounds (WCG) were developed;
PT

>WCG-containing composites enhanced the adsorption of pharmaceuticals from water;

E

>Maximum removal of pharmaceuticals was verified under mild experimental

CC

conditions;

>The composite shows acceptable reusability in consecutive adsorption processes.

A

Abstract
Waste coffee-grounds (WCG), a poorly explored source of biocompounds, were
combined with chitosan (Cs) and poly(vinyl alcohol) (PVA) in order to obtain
composites. Overall, WCG showed a good interaction with the polymeric matrix and
good dispersibility up to 10 wt-%. At 5 wt-% WCG, the composite exhibited a

1
noticeable enhancement (from 10 to 44%) of the adsorption of pharmaceuticals
(metamizol (MET), acetylsalicylic acid (ASA), acetaminophen (ACE), and caffeine
(CAF)) as compared to the pristine sample. The highest removal efficiency was
registered at pH 6 and the removal followed the order ASA > CAF > ACE > MET. For
all pharmaceuticals, the adsorption kinetics was found to follow the pseudo-second
order model, while the adsorption mechanism was explained by the Freundlich
isotherm. Reuse experiments indicated that the WCG-containing composite has an
attractive cost-effectiveness since it presented a remarkable reusability in at least five

T
consecutive adsorption/desorption cycles.

R IP
Keywords: chitosan; coffee grounds; chitosan composites; adsorption; pharmaceutical
contaminants; emerging contaminants.

SC
Chemical compounds studied in this article

U
Chitosan (PubChem CID: 71853); poly(vinyl alcohol) (PubChem CID: 3083375);
N
hydrochloric acid (PubChem CID: 313); glutaraldehyde (PubChem CID: 3485);
A
metamizol (PubChem CID: 3111); acetyl salicylic acid (PubChem CID: 2244);
M

acetaminophen (PubChem CID: 1983); caffeine (PubChem CID: 2519); sodium

ED

hydroxide (PubChem CID: 14798) and acetic acid (PubChem CID: 176).
PT

1. Introduction

The consumption of pharmaceutical compounds around the world has shown a

E

noticeable increase in the last years. The easy access and self-medication practices (i.e.
CC

administration of nonprescription medicines) have made the pharmaceuticals one of the

major classes of organic pollutants discharged into the environment (Gracia-Lor,

A

Sancho, Serrano, & Hernandez, 2012; Kostich, Batt, & Lazorchak, 2014). These

emerging contaminants have attracted widespread attention due to the issues related to

their removal from the contaminated surface, ground, and drinking water (der Beek et

al., 2016; Radjenovic, Petrovic, & Barcelo, 2007). Overall, pharmaceuticals and their

2
metabolites are excreted and enter in the urban wastewater treatment plants. Some of

these compounds are degraded during sewage treatment processes, while others are

eliminated by chemical or biological treatments (Jones, Voulvoulis, & Lester, 2005).

However, the complete elimination of these contaminants from wastewater is hardly

achieved (Jelic et al., 2011). Several studies have reported that even at low

concentration, pharmaceuticals cause toxic and adverse effects on humans (Larsson,

T
2014; A. Y. C. Lin, Wang, & Lin, 2010). Such risks can be increased due to the low

IP
biodegradability, high persistence, and facile bioaccumulation of these compounds

R
(Carucci, Cappai, & Piredda, 2006; Radjenovic et al., 2007). For these reasons,

SC
numerous efforts have been done to develop methods and devices capable to overcome

the shortcoming related to the removal of pharmaceuticals from water.

U
Adsorption has attracted particular attention as an efficient method for
N
wastewater treatment. This success can be associated with the advantages exhibited by
A

adsorption compared to other methods (e.g. simplicity, high removal rate, easy
M

operation and implementation, low cost, no sludge formation, and so on) (Arya &
ED

Philip, 2016; Zhang et al., 2016; Zhuo et al., 2017). Moreover, a wide range of materials

and devices (i.e. films, membranes, gels, particles, etc.) are applicable in the adsorption,
PT

which expands the possibilities of application (Basu & Balakrishnan, 2017; L. Lin,

Jiang, & Xu, 2017; Yoo, Seong, & Park, 2016). As noticed in the literature, the use of
E
CC

bio-based adsorbents, which are formulated by using the natural feedstock (e.g.

biopolymers and biocompounds), have gained special attention of the researchers in

A

developing wastewater treatment technologies. (Gomes et al., 2015; Lessa, Gularte,

Garcia, & Fajardo, 2017; Ngah, Teong, & Hanafiah, 2011). In general, biopolymers and

biocompounds show interesting features such as low-cost, renewability, and

availability. Additionally, the numerous functional groups present on their structures

3
enhance the adsorption capacity as compared to other compounds (Ciechanska,

Wietecha, Kucharska, Wrzegniewska-Tosik, & Kopania, 2014; Magdy, 2011).

Taking into account this information, here we report the synthesis of

chitosan/waste coffee-grounds based composites and their adsorption capacities for the

removal of pharmaceuticals from water. Chitosan (Cs) is a well-known chitin derivative

widely utilized in the formulation of adsorbent materials due to its attractive properties

T
(e.g. non-toxicity, biodegradability, biocompatibility, inexpensiveness, chemical

IP
resistance, stability, chelation, among others) (Rinaudo, 2008). Waste coffee-grounds

R
(WCG) are the main residue generated after coffee dripping. Million tons of such

SC
residue, which is composed of several constituents (water, cellulose, lignin,

hemicelluloses, fats, ashes, protein, and aliphatic acids), are produced every year
U
(Ballesteros, Teixeira, & Mussatto, 2014). The uncontrolled release of WCG in the
N
environment causes contamination since its decomposing consumes large quantities of
A

oxygen. Nowadays, reuse of WCG is limited to few applications, for example, as fuel
M

for industrial boilers, as a substrate for cultivation of microorganisms and as raw

ED

material to produce ethanol (Ballesteros, Ramirez, Orrego, Teixeira, & Mussatto, 2017;

Ballesteros et al., 2014; Ballesteros, Teixeira, & Mussatto, 2017; Mussatto, Machado,
PT

Carneiro, & Teixeira, 2012). Some studies report the use of WCG on the elimination of

dye and metal ions from water (Davila-Guzman et al., 2013; Roh et al., 2012).
E
CC

Nonetheless, there is no information about the use of WCG as an adsorbent for the

removal of pharmaceuticals. Therefore, in this study, WCG was associated with Cs

A

aiming to obtain a composite material with enhanced adsorption capacity. Poly(vinyl

alcohol) (PVA) was utilized in the composite formulation due to its filmogenic,

plasticizing and hydrophilic properties (Alves et al., 2016). Moreover, caffeine,

acetaminophen, acetylsalicylic acid, and metamizol were selected as pharmaceuticals

4
models. All of them are popular pharmaceuticals, commonly used in human and

veterinary medicine and frequently found in wastewater treatment plants (Gracia-Lor et

al., 2012; Kostich et al., 2014; Radjenovic et al., 2007).

2. Experimental section

2.1 Materials

T
Chitosan (Cs, 85% deacetylated, Mv 87,000 g/mol) was purchased from Golden-

IP
Shell Biochemical (China). Poly(vinyl alcohol) (PVA, 99% hydrolyzed, Mw 124,000

R
g/mol) and glutaraldehyde (25 wt/v-% in water) were purchased from Sigma-Aldrich

SC
(USA). Coffee-grounds were obtained from a local coffee brand (Brazil) composed of

100% Arabica beans. Acetic acid (99%) was purchased from Vetec (Brazil). Caffeine
U
(CAF), acetaminophen (ACE), acetylsalicylic acid (ASA) and metamizol (MET)
N
(pharmaceuticals purity >99%) were purchased from Hebei Jihengcompany (China). All
A

chemicals of analytical grade were used as received without further purification.

M
ED

2.2 Waste coffee-grounds preparation

Waste coffee-grounds (WCG) were collected after coffee dripping and, then,
PT

oven-dried at 100 ºC overnight. The dry WCG was thoroughly washed with portions

(~50 mL) of different solvents (hexane, ethanol, and distilled water) under magnetic
E
CC

stirring at room temperature in order to remove residual organics. After that, the

purified WCG was oven-dried (100 ºC, overnight) and sieved (80 mesh size) for further
A

utilization.

2.3 Synthesis of Cs/WCG composites

5
 The synthesis of the Cs/WCG composites was performed by solvent casting

method. Firstly, 750 mg of Cs was completely solubilized in 25 mL of acetic acid

solution (1.5 v/v-%). Then, the Cs solution was blended with a PVA solution (750 mg

of PVA solubilized in 30 mL of distilled water). The system (Cs/PVA) was

homogenized under magnetic stirring at room temperature for 30 min. Next, a specific

amount of WCG (0, 5, or 10 wt-% in respect to the dry mass of the polymers) was

T
added to the system, which was sonicated in an ultrasonic bath (15 min).

IP
Glutaraldehyde (52 μL) was added by drop wise and the filmogenic solution was gently

R
poured into a Petri dish (85 x 10 mm round-plate shape). Finally, the solvent was

SC
removed under vacuum (40 ºC for 24 h). Following the solvent casting, the Cs/WCG

composite was removed from the Petri dish, purified in distilled water, oven-dried (40
U
ºC overnight) and stored in a desiccator. The synthesized composites were labeled as
N
Cs/WCG0, Cs/WCG5, and Cs/WCG10, respectively.
A
M

2.4 Characterization
ED

Fourier transform infrared (FTIR) spectra were recorded on a Shimadzu IR

Affinity-1 spectrometer (Japan) operating in the range of 4000–400 cm-1 with a

PT

resolution of 4 cm-1 and 64 scans. Samples were ground with spectroscopic grade KBr

and, then, pressed into disks. X-ray diffraction (XRD) data were collected on a Siemens
E
CC

D-500 diffractometer (Germany) using the Cu-Kα radiation at 30 kV and 20 mA.

Thermogravimetric analysis (TGA) was recorded using a Shimadzu TGA-60 analyzer

A

(Japan) in a dry N2(g) atmosphere at a flow rate of 20 mL/min. Experiments were

performed from 25 ºC to 600 ºC with a heating rate of 10 ºC/min. Scanning electron

microscopy (SEM) images were recorded by a JEOL JSM-6610LV microscope (USA).

Before imaging, the samples were coated with a thin gold film. Mechanical properties

6
were examined by tensile tests using a texturometer equipment (Stable Microsystems

TA.XT2, UK) with composite samples cut in rectangular shape 80 x 25 mm (length x

width) in an atmosphere of 50% relative humidity with a test speed of 0.8 mm/min

according to the ASTM D882-12 method.

Liquid uptake capacity of the composites was investigated by swelling

experiments performed at different pH conditions. For this, dry samples were weighed

T
and then placed into flasks filled with distilled water (50 mL) at room temperature. The

IP
pH was set to different values (2–10) by using HCl (1.0 M) or NaOH (1.0 M) solutions.

R
At predetermined time intervals, the samples were withdrawn and weighed again. It is

SC
worth to say that the excess of liquid on the sample surfaces was carefully blotted off

before weighing. The swelling ratio was calculated by Eq. (1), where wd (g) is the
U
weight of the dry sample and ws (g) is the weight of the swollen sample at time t.
N
A

𝑤𝑠 − 𝑤𝑑
𝑠𝑤𝑒𝑙𝑙𝑖𝑛𝑔 (%) = 𝑥 100
M

(1)
𝑤𝑑
ED

2.5 Adsorption experiments

Batch adsorption experiments were conducted in 250 mL Erlenmeyer flasks

PT

filled with individual stock solutions of CAF, ACE, ASA, or MET (100 mL) placed on
E

an orbital shaker (100 rpm). Composite samples (50 mg) were added into the flasks and
CC

at predetermined time intervals aliquots (4 mL) were withdrawn and analyzed by using

an UV-Vis Micronal BS82 spectrometer (Brazil). After each measurement, the aliquots
A

were returned to the testing flasks. The residual concentration of each pharmaceutical in

solution was estimated using the UV absorbance data measured at the λmax (CAF - λmax

≈ 273 nm; ACE - λmax ≈ 243 nm; ASA - λmax ≈ 296 nm and MET - λmax ≈ 271 nm) and

the previously built calibration curves. All calibration curves obeyed a linear Beer-

7
Lambert relationship (R2 > 0.991). The percentage of pharmaceutical removal and the

amount of pharmaceutical adsorbed (mg) per gram of composite (qt) at time t was

calculated using Eq. (2) and (3):

(𝐶0 −𝐶𝑒𝑞 )
𝑅𝑒𝑚𝑜𝑣𝑎𝑙 (%) = 𝑥 100 (2)
𝐶0

(𝐶0 − 𝐶𝑡 )

T
𝑞𝑡 = 𝑉 (3)
𝑚

R IP
where C0 (mg/L) is the initial concentration of pharmaceutical in stock solution and Ceq

SC
(mg/L) is the residual concentration of pharmaceutical at equilibrium and Ct (mg/L) is

residual concentrations of pharmaceutical in stock solution at different time, m (g) is the

U
mass of the composite sample on a dry basis, and V (L) is the volume of solution. The
N
effects of pH (3, 6, and 9), initial pharmaceutical concentration (0.25–2 mg/L), and
A
temperature (25–55 ºC) on the adsorption process were investigated. All the
M

experiments were performed in triplicate (n = 3).

ED

2.6 Reuse experiments

PT

Reuse experiments were performed in order to investigate the robustness of the

WCG-containing composite in consecutive adsorption/desorption cycles. For adsorption

E

step, the composite sample (50 mg) was immersed in the pharmaceutical solution at
CC

selected optimal conditions (C0 2 mg/L, pH 6, 25 ºC) for 1 h. Next, the pharmaceutical-

loaded composite was recovered and immersed in the desorption solution

A

(ethanol/distilled water - volume ratio of 40:60 v/v-%) for 1 h at room temperature. The

regenerate composite was thoroughly washed with distilled water, oven-dried (40 ºC,

overnight) and, then, utilized in a novel adsorption/desorption cycle. The

8
pharmaceutical removal after each cycle was calculated by using Eq. (2). Again, all

experiments were conducted in triplicate (n = 3).

3. Results and discussion

3.1 Characterization

Figure 1a presents the FTIR spectra of WCG, Cs, PVA, and Cs/WCG

T
composites. As observed, WCG spectrum presented bands characteristic of

IP
lignocellulosic materials since its major constituents are hemicellulose, cellulose, lignin

R
and other small molecules (Ballesteros et al., 2014). The broadband centered at 3360

SC
cm-1 is related to the O-H stretching vibration and the bands between 2930–2860 cm-1

are related to the aliphatic C-H stretching vibration. The bands at 1728, 1647 and 1530
U
cm-1 are associated with the carbonyl C=O stretching of hemicellulose and chlorogenic
N
acids and stretching vibration of C-N bonds of caffeine (Ballesteros et al., 2014; Reis,
A

Franca, & Oliveira, 2013). Bands at 1450 and 1377 cm-1 are related to the CH2 and CH3
M

bending modes while the bands between 1240–1160 cm-1 results from the C-O-C bonds
ED

of lignin, chlorogenic acid, and caffeine. The broadband between 1100–990 cm-1 is

associated with the C-O-H bonds typical of polysaccharides (Heredia-Guerrero et al.,

PT

2014). Cs spectrum showed a broadband between 3700–3000 cm-1 related to the

stretching vibrations of O-H and N-H bonds and bands at 1660, 1598 and 1424 cm-1
E
CC

assigned to C=O stretching (amide I), N-H deformation vibration (amide II) and

stretching vibration of C-N bonds (Alves et al., 2016). Bands between 1160–990 cm-1
A

are related to the C-C, C-O-C and C-OH bonds from glycosidic linkages (Alves et al.,

2016; Kloster, Marcovich, & Mosiewicki, 2015). PVA exhibited a broadband centered

at 3460 cm-1 assigned to O-H stretching vibration and bands between 3000–2800 cm-1

related to the alkyl C-H stretching vibration. The bands at 1710 and 1100 cm-1 are

9
attributed to the C=O stretching vibration of residual acetate groups and C-O bonds

(Huang et al., 2012). The FTIR spectrum of Cs/WCG0 showed the typical bands of Cs

and PVA, although some discrepancies regarding the raw polymers are noticed due to

crosslinking reaction with glutaraldehyde. The chemical crosslinking of Cs and PVA

with glutaraldehyde converts the amino groups of Cs into imine groups (C=N) and

forms acetal rings with PVA (Li, Cheng, & Yan, 2007). The shoulder-like band at 1626

T
cm-1 observed in the Cs/WCG0 spectrum is related to the stretching vibration of C=N

IP
bonds and the band between 1150–990 cm-1 attributed to the stretching vibrations of C-

R
O and C-O-C bonds is broaden due to the acetal ring (Li et al., 2007). In addition, the

SC
O-H and N-H stretching vibration band (3700–3000 cm-1) of Cs/WCG0 spectrum was

decreased in intensity when compared to raw Cs and PVA. On contrary, bands between
U
2930–2850 cm-1 and 1430–1380 cm-1 related to the stretching vibration and bending
N
mode of C-H bonds increased in intensity due to the CH2 groups of glutaraldehyde (de
A

Souza, da Silva, & Fajardo, 2017). From this data, it can be suggested that both Cs and
M

PVA were chemically crosslinked by glutaraldehyde resulting in a full-interpenetrating

ED

network (IPN) film. The Cs/WCG5 and Cs/WCG10 spectra exhibited small differences

in comparison to Cs/WCG0 spectrum. The broadband associated with the O-H and N-H
PT

stretching vibration (3700–3000 cm-1) was shifted to lower wavenumber region, which

suggests that the hydrogen bonds interactions between the two polymers reduce due to
E
CC

the presence of WCG. Moreover, the bands related to the C-H bonds (stretching

vibration and bending mode) increased in intensity when compared to Cs/WCG0

A

spectra likely due to the CH2 and CH3 groups of WCG constituents (hemicellulose,

lignin, etc.). To confirm the formation of Cs/WCG composites, their structure was

investigated by XRD analysis (Figure 1b). The diffraction pattern of WCG exhibited

two broad peaks centered at 2θ ≈ 15.6º and 22.1º, which can be associated with

10
cellulosic materials present in WCG (Ballesteros et al., 2014; Rivera et al., 2011). In

contrast, hemicellulose and other constituents of WCG have an amorphous structure

(Ballesteros et al., 2014). According to the literature, Cs and PVA have some

crystallinity due to the hydrogen bonds formed among its functional groups. The Cs

crystallinity index depends on its deacetylation degree (Kumirska et al., 2010). The

XRD pattern of Cs/WCG0 exhibited two diffraction peaks centered at 2θ ≈ 19.5º and

T
40.6º suggesting that these samples show semi-crystallinity likely due to the PVA

IP
moiety. Similar results are reported for Cs/PVA blends crosslinked by glutaraldehyde

R
(de Souza et al., 2017; Tripathi, Mehrotra, & Dutta, 2009). The XRD patterns of

SC
Cs/WCG5 and Cs/WCG10 revealed the diffraction peaks proceeding from the Cs/PVA

matrix and the typical diffraction peaks of WCG (at 2θ ≈ 15.6º and a shoulder-like peak
U
around 2θ ≈ 23º). Besides, these diffraction peaks increase in intensity as the amount of
N
WCG in the composite increases. These findings confirm the formation of Cs/WCG
A

composites. Moreover, the absence of other diffraction peaks in the XRD pattern of
M

Cs/WCG5 and Cs/WCG10 implies that any ordered structures result from the polymers-
ED

WCG interactions. This weak interaction among the polymeric matrix and WCG

explains the FTIR data.

E PT
CC
A

Figure 1

11
 TGA analysis was utilized to investigate the effect of the WCG on the thermal

stability of the Cs/PVA matrix (Figure 2a). The TGA curve of WCG showed three

defined weight loss stages. The first one occurs in the temperature range of 25–90 ºC

and corresponds to the water evaporation and release of light volatile compounds. A

weight loss of about 7.7% for WCG was observed at this stage. The second stage (200 –

T
400 ºC) corresponds to the highest weight loss (~56.2%) due to the depolymerization

IP
and decomposition of polysaccharides and some fats present in WCG. DTG peaks

R
observed at 311 ºC and 334 ºC are the thermal decomposition temperatures of

SC
hemicellulose and cellulose (Ballesteros et al., 2014; Poletto, Dettenborn, Pistor, Zeni,

& Zattera, 2010) (Figure 2b). The third and last stage (ca. 450 ºC) exhibited a weight
U
loss of ~14.1% and it can be assigned to the formation of carbonaceous materials and
N
consolidation of carbon structures. The residue at 600 ºC for WCG was approximately
A

22%. The TGA curve recorded to Cs/WCG0 exhibited four weight loss stages. The first
M

weight loss stage at 109 ºC (~6.8%) is due to water evaporation (i.e. dehydration), while
ED

the second and third weight losses at 282 ºC and 363 ºC are related to the thermal

decomposition of linear and crosslinked moieties of Cs and PVA. The fourth weight
PT

loss stage at 434 ºC is associated with the polyene backbone degradation of PVA (Yang,

Xu, Jiang, & Dan, 2012). The composites, Cs/WCG5 and Cs/WCG10, exhibited TGA
E
CC

curves comparable to that recorded to Cs/WCG0, although some discrepancies can be

noticed. The presence of WCG in the polymer matrix reduces the weight loss credited to
A

the dehydration process, which suggests that WCG affects the interactions among the

polymer matrix and water molecules. Furthermore, it was observed that the temperature

of the first weight loss stage increases to higher values as the content of WCG into the

composite increases. Probably, WCG reduces the amount of physisorbed water, which

12
is eliminated in lower temperatures. Moreover, as demonstrated by DTG analysis all the

temperatures associated with the different weight loss stages of Cs/WCG0 are

influenced by the WCG presence. These findings allow suggesting that this filler affects

the interactions between the polymers. Moreover, the DTG curve of Cs/WCG10

exhibited a shoulder-like peak around 310 ºC assigned to WCG, which confirms its

incorporation into the polymer matrix.

T
R IP
SC
U
N
A
M

Figure 2
ED
E PT
CC
A

Figure 3

13
 Photographic images taken of the composites are presented in Figure 3(a-c). The

surface morphology of Cs/WCG composites was investigated by SEM images. From

Figure 3a, is possible to observe that Cs/WCG0 showed a homogeneous and continuous

surface indicating the absence of phase separation and the good compatibility between

Cs/PVA. This smooth surface is slightly affected by the addition of 5 wt-% of WCG as

T
clearly demonstrated in Figure 3b. The absence of aggregates suggests good

IP
compatibility between the polymers and the filler at this concentration. The increase of

R
WCG content into the composite promotes visible changes in the composite

SC
morphology. Cs/WCG10 composite showed higher roughness as compared to the other

samples and it is noticed that some aggregates are distributed heterogeneously on the
U
composite surface (Figure 3c). Probably, high WCG content harms the compatibility
N
between the polymer matrix and the filler and for this reason the maximum content of
A

WCG utilized in the composite formulation was fixed in 10 wt-%.

M

The effect of the different amounts of WCG on the mechanical properties of the
ED

composites was investigated and the results are presented in Table 1. At 5 wt-% WCG

the composite exhibits an obvious increase in tensile strength and Young´s modulus as
PT

compared to Cs/WCG0. The tensile strength value of Cs/WCG5 was increased by 33%

compared to Cs/WCG0, while the Young´s modulus was increased by 172%.

E
CC

Conversely, the elongation at break decreased by 51%. These results indicate that WCG

act as a reinforcement agent likely due to the non-electrostatic interactions that are
A

engaged between WCG and the polymeric matrix. Moreover, the good dispersibility of

the WCG in the polymeric matrix amplifies this reinforcement effect. The WCG-

polymeric matrix interactions act as additional crosslinking points, which make the

composite harder than the pristine sample. At 10 wt-% WCG, the mechanical properties

14
of the composite did not show significant improvement regarding the sample containing

5 wt-% of WCG. As demonstrated by previous analysis, high amounts of WCG are not

efficiently distributed in the polymeric matrix, which can explain these findings.

T
IP
Table 1. Mechanical properties of Cs/WCG composites.

R
Tensile strength Elongation at break Young´s modulus

SC
Sample
(MPa) (%) (MPa)

Cs/WCG0 28.2 ± 3.0 8.6 ± 0.8 32.9 ± 3.0

Cs/WCG5
Cs/WCG10
37.6 ± 4.2
41.2 ± 5.3 U
4.2 ± 0.4
4.0 ± 0.6
89.5 ± 6.8
103.0 ± 8.3
N
A
The understanding of swelling properties and kinetics is essential to design an
M

efficient adsorbent material. Moreover, the effect of external factors on this property
ED

should be investigated since the adsorption process is enhanced or harmed according to

the experimental conditions (Dabrowski, 2001). Herein, the swelling profile of the
PT

Cs/WCG composites was investigated under different pHs (Figure S1). Overall, all

samples showed similar swelling behavior under the tested pH conditions. The highest
E

swelling values were achieved under acidic conditions (pH ≤ 4) while close to neutrality
CC

and under alkaline conditions the uptake capacity is reduced. Acidic conditions promote

the protonation of the amino groups of Cs increasing the cation-cation repulsive forces
A

within the composite matrix. These repulsive forces favor the expansion of the

composite matrix contributing to the liquid influx and diffusion through the polymer

network. As result, the swelling is enhanced under acidic conditions. Close to neutrality

(pH ~6) or under alkaline conditions (pH > 8) the amino groups are not charged, which

15
reduces the network expansion and restricts the liquid sorption. As noticed, the WCG

added within the polymer matrix reduces the swelling discrepancies among the different

pH conditions. Furthermore, the samples Cs/WCG5 and Cs/WCG10 showed lower

swelling ability than the Cs/WCG0 sample, which can be attributed to the interaction

among the functional groups of WCG (i.e. hydroxyl and carbonyl) and Cs/PVA mainly

by H-bonding. This interaction decreases the availability of hydrophilic groups to

T
interact with the water molecules and act as additional crosslinking points, which

IP
restrict the matrix expansion. In addition, it is worth to note that the samples Cs/WCG0

R
and Cs/WCG5 showed a fast swelling rate during the first minutes of immersion and

SC
they achieved the swelling equilibrium around 30 min at all conditions tested. After this

time, the swelling curves did not show obvious variation until to the end of the
U
experiment. In contrast, the Cs/WCG10 composite achieved the swelling equilibrium
N
earlier than the other samples (ca. 20 min). Clearly, the WCG presence affects the
A

swelling kinetics of the composites.

M
ED

3.2 Adsorption experiments

The effect of the composite formulation and pH on the adsorption of tested

PT

pharmaceuticals (MET, ASA, ACE, and CAF) was investigated (Figure 4a-c). As

observed, the sample formulated without WCG (i.e. Cs/WCG0) showed the lowest
E
CC

removal capacity for all tested pHs and pharmaceuticals (Figure 4a). The superior

performance demonstrated by the composites can be attributed to the incorporation of

A

WCG within the Cs/PVA matrix, which increases the number of adsorption sites on the

composites and favors the pharmaceuticals adsorption. The functional groups (–OH, –

NH, –COOH) and the carbonic (aliphatic and aromatic) backbone of the WCG

components (cellulose, lignin, hemicellulose, chlorogenic acid, etc.) strength the

16
interaction between the pharmaceuticals and WCG-based composites due to extra H-

bonds, van der Waals, and hydrophobic forces. Moreover, the adsorption experiments

showed that the composite Cs/WCG5 has higher improvement regarding the removal

capacity than Cs/WCG10 (Figure 4b and c). As aforementioned, at 10 wt-% the high

content of WCG affects its distribution through the polymeric matrix resulting in small

aggregates. Such aggregates reduce the number of adsorption sites on the Cs/WCG10

T
composite explaining the slight decrease in the removal of the four pharmaceuticals as

IP
compared to Cs/WCG5.

R
SC
U
N
A
M
ED
E PT
CC

Figure 4
A

In addition, as clearly demonstrated here, the removal efficiency varied

according to the pharmaceutical type (Figure S2 shows the chemical structure of each

one). However, for all composites the adsorption efficiency followed the order ASA >

17
CAF > ACE > MET. Overall, the MET removal was the less efficient probably due to

its high molecular weight compared to the other pharmaceuticals. Moreover, the pH of

the medium has a considerable effect on its removal. Under acidic conditions (pH 3) the

sulfonate group (–SO3-) of MET is protonated decreasing its interaction with the

adsorbent matrix. With the pH increase (pH ≥ 6) the sulfonate group of MET is

deprotonated and its adsorption increases. On the other hand, the ASA removal showed

T
remarkable efficiency (>85%) for all tested composites and pH conditions. The pKa of

IP
ASA is 3.49 (Lin & Blake, 1966) which favors its deprotonation at pH higher than 3.

R
The negatively charged carboxyl groups of ASA, as well as its hydrophilic groups,

SC
enhance its adsorption on the composites. Taking into account the ACE and CAF

removal, for both pharmaceuticals the adsorption was improved under pH > 3. Such
U
improvement regarding the ACE and CAF removal was more evident for Cs/WCG0 and
N
Cs/WCG10. Under acidic conditions, the amino groups of Cs are protonated (–NH3+)
A

and due to its charged nature the composite matrix expands and the non-electrostatic
M

interactions (H-bonds, van der Waals bonds, hydrophobic bonds, and so on) are
ED

weakened. With the pH increase, the amino groups of Cs, which shows a pKa of 6.5, are

deprotonated favoring the pharmaceuticals-composite interactions. As aforementioned,

PT

at 5 wt-% WCG is well distributed into the composite matrix. Therefore, under neutral

and alkaline conditions its interaction with the composite matrix increases and, as result,
E
CC

the pharmaceuticals adsorption decrease. This explains the decreasing in the

pharmaceuticals removal by the Cs/WCG5 composite at pH 9 as compared to the other

A

samples. It is worthy to inform that after each adsorption experiment the pH of the

medium was measured and the pH variation was negligible for all tested conditions. So,

these results indicated that Cs/WCG5 was the most efficient adsorbent for removal of

these pharmaceuticals from water and pH 6 was the optimum pH condition (Figure 4b).

18
This pH value is close to the pH of natural waters, which suggests that Cs/WCG5 can be

directly applied to pharmaceutical removal without any pH adjustment reducing the

practical application costs.

3.2.1 Adsorption kinetics

Adsorption kinetics was studied varying the initial concentration of each

T
pharmaceutical and fixing the other experimental conditions. The results presented in

IP
Figure 5(a-d) reveal that for all pharmaceuticals, the increasing of initial concentration

R
from 0.25 to 2 mg/L increases the qt values dramatically. Moreover, the amount of

SC
pharmaceutical adsorbed per gram of Cs/WCG5 increased fast during the first 30 min of

exposition. This behavior can be assigned to the instantaneous adsorption of these

U
pharmaceuticals on the Cs/WCG5 surface and, as evidenced, it is more pronounced for
N
ASA and CAF. For all cases, the adsorption rate slows down between the 30 and 40 min
A

of exposition and the adsorption equilibrium (qe) is achieved close to 60 min.

M

Concomitantly, the adsorption efficiency followed the order ASA > CAF > ACE >
ED

MET at all concentration tested, corroborating the previous adsorption experiments.

E PT
CC
A

19
 T
IP
Figure 5

R
SC
To evaluate the kinetic adsorption mechanism different kinetic models were

employed to fit the experimental data. In this sense, pseudo-first order, pseudo-second

U
order, Elovich´s and intra-particle diffusion models were utilized (detailed explanation
N
of these kinetic models is provided in the Supporting Information) (Lagergren & S.,
A
1898; Rodrigues & Silva, 2016; Wu, Tseng, Huang, & Juang, 2009; Zeng et al., 2015).
M

As result, the pseudo-second order model showed the highest R2 values suggesting that

this model is adequate to explain the kinetics data. Moreover, an error function, the non-
ED

linear Chi-square (χ2) determination (Eq. 8), was utilized to evaluate the fit of the

pseudo-second order model to the experimental data (Subramanyam & Das, 2014).
E PT

2
2 (𝑞𝑒(𝑒𝑥𝑝) −𝑞𝑒(𝑐𝑎𝑙) )
𝜒 =∑ (8)
CC

𝑞𝑒(𝑐𝑎𝑙)
A

where qe(exp) (mg/g) is the amount of pharmaceutical adsorbed per gram of adsorbent at

equilibrium under the tested experimental conditions and qe(cal) (mg/g) is a theoretical

value calculated from the pseudo-second order model. As demonstrated in Table 2, the

small χ2 values suggest a good agreement between the data calculated from the pseudo-

20
second order model and the experimental data confirming that this model is the best-

fitting model to the kinetics data shown in Figure 5.

T
R IP
Table 2. Pseudo-second order kinetic parameters for the adsorption of pharmaceuticals

SC
on Cs/WCG5.
C0
Pharmaceutical Parameter

qe(exp)a (mg/g)
2 mg/L
U
1 mg/L 0.5 mg/L 0.25 mg/L
N
6.29 3.40 1.71 0.92
qe(cal)b (mg/g) 6.42 3.49 1.75 0.94
A
MET k2 (g/mg min) 0.05 0.08 0.21 0.47
M

R2 0.999 0.998 0.999 0.998

χ2 0.003 0.002 0.001 0.001
ED

qe(exp)a (mg/g) 9.92 4.92 2.46 1.21

qe(cal)b (mg/g) 10.38 5.38 2.39 1.45
PT

ASA k2 (g/mg min) 0.13 0.17 0.21 0.29

R2 0.998 0.999 0.999 0.997
χ2 0.020 0.039 0.002 0.040
E

qe(exp)a (mg/g) 7.52 3.89 1.79 0.92

CC

qe(cal)b (mg/g) 7.19 4.01 2.02 0.96

ACE k2 (g/mg min) 0.03 0.07 0.11 0.15
A

R2 0.999 0.999 0.999 0.996

χ2 0.015 0.004 0.026 0.002
qe(exp)a (mg/g) 8.21 4.09 2.06 1.08
CAF qe(cal)b (mg/g) 8.66 4.44 2.56 1.28
k2 (g/mg min) 0.06 0.13 0.27 0.56

21
 R2 0.999 0.999 0.998 0.999
χ2 0.023 0.036 0.098 0.031
a
Experimental data; b theoretical data.

Pseudo-second order model indicates chemisorption between the

pharmaceuticals and the Cs/WCG5 composite and the number of active sites on the

adsorbent determines the adsorption capacity. In this case, it is supposed that valence

T
IP
forces are involved likely due to sharing or exchanging of electrons between the

adsorbent and the adsorbate (Moussawi & Patra, 2016; Zhang et al., 2016). This

R
explains the highest adsorption of ASA as compared to the other pharmaceuticals.

SC
Studies on the adsorption of pharmaceuticals on biopolymer and biopolymer derivatives

U
are commonly described by the pseudo-second order models, as reported elsewhere
N
(Zhang et al., 2016; Zhuo et al., 2017). Table 3 displays a comparative chart of MET,
A
ASA, ACE, and CAF adsorption on different adsorbents. The composite Cs/WCG5
M

shows comparable or even better adsorption capacity than other adsorbents reported

elsewhere. Moreover, Cs/WCG5 exhibits a fast adsorption kinetics (< 1 h) under mild
ED

conditions and compared to other adsorbents (e.g. graphene, activated carbon, and

zeolites) our eco-friendly adsorbent has a low-cost processing. All these aspects are of
PT

interest from the practical viewpoint.

E
CC
A

22
 T
R IP
Table 3. Pharmaceuticals adsorption on different adsorbents comparative chart.

SC
Experimental conditions
qe
Pharmaceutical Adsorbent C0 Time Temp. Ref.
(mg/g) pH
(mg/L) (h) (ºC)
Metamizol Cs/WCG5 6.29 2 6
U 0.67 25 this work
N
(Carvalho, Matias,
Chitosan Braga,
Metamizol 150.38 2000 - 24 25
A
microspheres Evangelista, &
Prado, 2011)
M

Acetylsalicylic
Cs/WCG5 9.92 2 6 0.67 25 this work
acid
(Al-Khateeb,
ED

Acetylsalicylic Graphene
18.07 20 8 1 25 Almotiry, &
acid nanoplatelets
Salam, 2014)
Acetylsalicylic Oxide-mesoporous (Teo, Siah, &
6.19 500 6 24 25
PT

acid silica MCM-41 Yuliati, 2016)

Cellulose acetate
imprinted membrane
Acetylsalicylic (Meng et al.,
E

assisted with 5.62 100 - 3 25

acid 2015)
chitosan-wrapped
CC

MWCNT
(Coimbra, Calisto,
Acetylsalicylic Pyrolyzed pulp mill
8.36 100 - 7 25 Ferreira, Esteves,
acid sludge
A

& Otero, 2015)

Acetaminophen Cs/WCG5 7.52 2 6 0.67 25 this work
Graphene (Al-Khateeb et al.,
Acetaminophen 12.98 20 8 1 25
nanoplatelets 2014)
Pyrolyzed pulp mill (Coimbra et al.,
Acetaminophen 13.31 100 - 7 25
sludge 2015)
Acetaminophen Clinoptilolite 1.57 0.1 - 24 24 (Leal, Martinez-

23
 Hernandez, Meffe,
Lillo, & de
Bustamante,
2017)
Acetaminophen Palygorskite 1.48 0.1 - 24 25 (Leal et al., 2017)
Caffeine Cs/WCG5 8.21 2 6 0.67 25 this work

Caffeine Clinoptilolite 1.65 0.1 - 24 24 (Leal et al., 2017)

Caffeine Palygorskite 0.27 0.1 - 24 25 (Leal et al., 2017)
Graphene (Al-Khateeb et al.,
Caffeine 19.72 20 8 1 25
nanoplatelets 2014)

T
Poly(N-isopropyl

IP
(Chern, Lee, &
Caffeine acrylamide) 10.70 0.5 - 720 25
Hsieh, 2004)
hydrogels

R
*Metamizol - MET; Acetylsalicylic acid - ASA; Acetaminophen - ACE; Caffeine - CAF.
3.2.2 Adsorption isotherm and thermodynamics

SC
The adsorption mechanism of the selected pharmaceuticals on the Cs/WCG5

U
composite was investigated from the microscopic viewpoint by using isotherms and
N
thermodynamics. Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherm
A
models were selected to fit the experimental data at equilibrium (detailed explanation of
M

these isotherm models is provided in the Supporting Information) (Dabrowski, 2001;

Lessa et al., 2017; Subramanyam & Das, 2014; Zheng, Zhu, & Wang, 2014). Based on
ED

the R2 values (Table 3), the Freundlich isotherm was the best-fitting model for all

pharmaceuticals. This isotherm is an empirical model commonly employed to describe

PT

heterogeneous systems. Furthermore, multilayer adsorption of these pharmaceuticals on

E

Cs/WCG5 surface is suggested by this isotherm model. As noted in Table 4, for all
CC

pharmaceuticals the n value was higher than unity indicating a favorable adsorption

(Saad, Khiari, Elaloui, & Moussaoui, 2014). Moreover, the KF values, which are related
A

to adsorption capacity, followed the order ASA > CAF > ACE > MET corroborating

with the experimental finds.

24
Table 4. Freundlich isotherm parameters for the adsorption of pharmaceuticals on
Cs/WCG5 at 25 ºC.
Pharmaceutical KF (mg/g)(L/mg)1/n 1/n n R2
MET 17.11 0.96 1.04 0.989
ASA 19.30 0.89 1.12 0.997
ACE 18.10 0.91 1.10 0.995
CAF 18.36 0.96 1.04 0.986

T
IP
Equilibrium thermodynamics parameters (Gº, Hº, and Sº) related to the

pharmaceuticals adsorption process were calculated (Table S1) (a detailed explanation

R
SC
about this procedure is provided in the Supporting Information) (Vaz, Pereira, Fajardo,

Azevedo, & Rodrigues, 2017; Yan et al., 2015). Negative values of Gº indicate that

U
the adsorption processes are spontaneous. As noticed, the adsorption of ASA and ACE
N
on Cs/WCG5 is spontaneous at the different temperature conditions. It is surprisingly
A
found that at high temperature (328 K) the adsorption of MET and CAF on the
M

adsorbent is not spontaneous, as demonstrated by the positive values of Gº. Probably,

at high temperature, MET and CAF molecules show enhanced solubility in water and
ED

the solvent-adsorbate interactions impair their adsorption on the Cs/WCG5 (Savjani,

PT

Gajjar, & Savjani, 2012). For all pharmaceuticals, the adsorption processes performed at

298 K are the most favorable, which is a very attractive advantage from the practical
E

viewpoint. Furthermore, all adsorption processes are guided by an exothermic process

CC

(Hº < 0). Low Hº values suggest that weak energy is involved in the adsorption of

these pharmaceuticals on Cs/WCG5 (El-Bindary, El-Sonbati, Al-Sarawy, Mohamed, &

A

Farid, 2014; Myers, 2002). Moreover, the adsorption of these pharmaceuticals promotes

a reordering on the Cs/WCG5 surface since the entropy decreased (Sº < 0). Overall,

negative values of Sº indicate reduced randomness at the composite/solution interface

25
whereas no significant changes occur in the internal structure of the composite through

the adsorption process (Saha, Chowdhury, Gupta, & Kumar, 2010).

3.3 Characterization of post-utilized adsorbent

FTIR spectra of Cs/WCG5 before and after adsorption of pharmaceuticals

(MET, ASA, ACE, and CAF) were recorded and they are shown in Figure 6a.

T
Compared to the Cs/WCG5 composite before adsorption, the spectra of

IP
pharmaceuticals-loaded composite showed few changes, which corroborate the

R
suggestion that weak forces are involved in the pharmaceuticals adsorption process.

SC
Overall, after pharmaceutical adsorption, the band assigned to the O-H stretching is

broadened and shifted to low wavenumber indicating the H-bond formation between the
U
hydroxyl groups of Cs/WCG5 and the pharmaceuticals. In the wavenumber region of
N
1700-1600 cm-1 some changes are observed due to the stretching of the C=O groups of
A

Cs/WCG5, which also interacts with the pharmaceuticals, and the C=O groups of
M

proceeding from the pharmaceuticals (ASA, ACE, and CAF). The spectra of the
ED

pharmaceutical-loaded Cs/WCG5 revealed bands at 1570 and 1426 cm-1 associated with

the aromatic C=C stretching and –CH3 out-of-plane bending vibrations. Furthermore,
PT

the bands in the 1150-1000 cm-1 show some change as compared to the Cs/WCG5

spectrum due to the stretching of the C-OH, C-O, C-O-C, and C-N bonds of the
E
CC

pharmaceuticals. In particular, the Cs/WCG5-MET spectrum exhibited a band at 1241

cm-1 assigned to the S=O stretching of the sulfate group of MET (Carvalho et al., 2011).
A

All these pieces of evidence confirm that weak interaction takes place among the

pharmaceuticals and the functional groups of Cs/WCG5 corroborating with the isotherm

and thermodynamic data.

26
 T
IP
Figure 6

R
SC
3.4 Reuse experiments

U
As demonstrated in Figure 6b, the removal efficiency of the pharmaceuticals
N
from water by using Cs/WCG5 as adsorbent showed slight decrease even after 5
A
consecutive adsorption/desorption cycles. Compared to the first cycle, the removal
M

efficiency at the last cycle decreased at about 9% for MET, 7% for ASA, 13% for ACE,

and 4% for CAF. These results suggest that the desorbing solution was more effective to
ED

regenerate the adsorption sites occupied by CAF and ASA. An inefficient desorption

process may result in a reduction of the adsorbent reusability. Overall, reuse

PT

experiments demonstrated that the removal efficiency for all tested pharmaceuticals is
E

stable at significant levels after consecutive adsorption/desorption cycles confirming the

CC

robustness of the Cs/WCG5 composite for practical wastewater treatment applications.

It should be mentioned here that the Cs/WCG5 handling, utilization, and recovery was
A

extremely simple, which is a remarkable advantage as compared to other adsorbents

reported in the literature. Simple and non-onerous processes were utilized here, which

strengthen the eco-friendly nature of our composite.

27
4. Conclusions

Composites containing different amounts of waste coffee grounds (WCG) were

synthesized by combing this residue with chitosan (Cs) and poly(vinyl alcohol) (PVA).

As demonstrated, up to 10 wt-% of WCG within the Cs/PVA matrix assures a good

distribution of this filler and a good interaction with the polymeric network. The

adsorption ability of these composites was tested towards the removal of

T
pharmaceuticals from water. At 5 wt-% WCG, the composite exhibited a noticeable

IP
enhancement (from 10 to 44%) on the adsorption of selected pharmaceuticals (MET,

R
ASA, ACE, and CAF) as compared to the pristine sample. It is suggested that the

SC
presence of WCG into the Cs/PVA matrix increases the number of adsorption sites on

the adsorbent surface favoring the adsorption process. Overall, highest removal
U
efficiency was registered at pH 6 and the removal followed the order ASA > CAF >
N
ACE > MET. For all pharmaceuticals tested, the adsorption kinetics was found to
A

follow the pseudo-second order model, while the adsorption mechanism was explained
M

by the Freundlich isotherm. Calculated thermodynamics confirms that the adsorption of

ED

these selected pharmaceuticals on the Cs/WCG5 is favorable. Reuse experiments

indicated that the WCG-containing composite has an attractive cost-effectiveness since

PT

it presented remarkable reusability in at least five consecutive adsorption/desorption

cycles. Taken together, these results allow inferring that WCG-containing composites
E
CC

can be utilized as promising low-cost and eco-friendly adsorbents for the removal of

pharmaceuticals from wastewater.

A

Acknowledgements

28
 The authors are thankful to CNPq and CAPES for the financial support

(Universal grant. - Process 441888/2014-3 and PQ fellowship - Process 305974/2016-

5).

Appendix A. Supplementary information

Supplementary information associated with this manuscript was submitted as a

T
separated file.

R IP
SC
References U
N
Al-Khateeb, L. A., Almotiry, S., & Salam, M. A. (2014). Adsorption of pharmaceutical
A
pollutants onto graphene nanoplatelets. Chemical Engineering Journal, 248, 191-
M

199.
Alves, N. O., da Silva, G. T., Webber, D. M., Luchese, C., Wilhem, E. A., & Fajardo,
ED

A. R. (2016). Chitosan/poly(vinyl alcohol)/bovine bone powder biocomposites: A

potential biomaterial for the treatment of atopic dermatitis-like skin lesions.
Carbohydrate Polymer,s 148, 115-124.
PT

Arya, V., & Philip, L. (2016). Adsorption of pharmaceuticals in water using Fe3O4
coated polymer clay composite. Microporous and Mesoporous Materials, 232, 273-
E

280.
CC

Ballesteros, L. F., Ramirez, M. J., Orrego, C. E., Teixeira, J. A., & Mussatto, S. I.
(2017). Optimization of autohydrolysis conditions to extract antioxidant phenolic
A

compounds from spent coffee grounds. Journal of Food Engineering, 199, 1-8.
Ballesteros, L. F., Teixeira, J. A., & Mussatto, S. I. (2014). Chemical, functional, and
structural properties of spent coffee grounds and coffee silverskin. Food and
Bioprocess Technology, 7, 3493-3503.

29
Ballesteros, L. F., Teixeira, J. A., & Mussatto, S. I. (2017). Extraction of
polysaccharides by autohydrolysis of spent coffee grounds and evaluation of their
antioxidant activity. Carbohydrate Polymers, 157, 258-266.
Basu, S., & Balakrishnan, M. (2017). Polyamide thin film composite membranes
containing ZIF-8 for the separation of pharmaceutical compounds from aqueous
streams. Separation and Purification Technology, 179, 118-125.
Carucci, A., Cappai, G., & Piredda, M. (2006). Biodegradability and toxicity of
pharmaceuticals in biological wastewater treatment plants. Journal of

T
Environmental Science and Health Part a-Toxic/Hazardous Substances &

IP
Environmental Engineering, 41, 1831-1842.

R
Carvalho, T. O., Matias, A. E. B., Braga, L. R., Evangelista, S. M., & Prado, A. G. S.
(2011). Calorimetric studies of removal of nonsteroidal anti-inflammatory drugs

SC
diclofenac and dipyrone from water. Journal of Thermal Analysis and Calorimetry,
106, 475-481.

U
Chern, J. M., Lee, W. F., & Hsieh, M. Y. (2004). Absorption isotherm of caffeine and
N
release kinetics from swollen NIPAAm hydrogels: Experiments and modeling.
Industrial & Engineering Chemistry Research, 43, 6150-6156.
A
Ciechanska, D., Wietecha, J., Kucharska, M., Wrzegniewska-Tosik, K., & Kopania, E.
M

(2014). Biomass as a source of functional polymeric materials. Polimery, 59, 383-

392.
ED

Coimbra, R. N., Calisto, V., Ferreira, C. I. A., Esteves, V. I., & Otero, M. (2015).
Removal of pharmaceuticals from municipal wastewater by adsorption onto
PT

pyrolyzed pulp mill sludge. Arabian Journal of Chemistry, 12, 1-12.

Dabrowski, A. (2001). Adsorption - From theory to practice. Advances in Colloid and
Interface Science, 93, 135-224.
E

Davila-Guzman, N. E., Cerino-Cordova, F. D., Soto-Regalado, E., Rangel-Mendez, J.

CC

R., Diaz-Flores, P. E., Garza-Gonzalez, M. T., & Loredo-Medrano, J. A. (2013).

Copper biosorption by spent coffee ground: equilibrium, kinetics, and mechanism.
A

Clean-Soil Air Water, 41, 557-564.

de Souza, J. F., da Silva, G. T., & Fajardo, A. R. (2017). Chitosan-based film supported
copper nanoparticles: A potential and reusable catalyst for the reduction of aromatic
nitro compounds. Carbohydrate Polymers, 161, 187-196.

30
der Beek, T. A., Weber, F. A., Bergmann, A., Hickmann, S., Ebert, I., Hein, A., &
Kuster, A. (2016). Pharmaceuticals in the environment-global occurrences and
perspectives. Environmental Toxicology and Chemistry, 35, 823-835.
El-Bindary, A. A., El-Sonbati, A. Z., Al-Sarawy, A. A., Mohamed, K. S., & Farid, M.
A. (2014). Adsorption and thermodynamic studies of hazardous azocoumarin dye
from an aqueous solution onto low cost rice straw based carbons. Journal of
Molecular Liquids, 199, 71-78.
Gomes, R. F., de Azevedo, A. C. N., Pereira, A. G. B., Muniz, E. C., Fajardo, A. R., &

T
Rodrigues, F. H. A. (2015). Fast dye removal from water by starch-based

IP
nanocomposites. Journal of Colloid and Interface Science, 454, 200-209.

R
Gracia-Lor, E., Sancho, J. V., Serrano, R., & Hernandez, F. (2012). Occurrence and
removal of pharmaceuticals in wastewater treatment plants at the Spanish

SC
Mediterranean area of Valencia. Chemosphere, 87, 453-462.
Heredia-Guerrero, J. A., Benitez, J. J., Dominguez, E., Bayer, I. S., Cingolani, R.,

U
Athanassiou, A., & Heredia, A. (2014). Infrared and Raman spectroscopic features
N
of plant cuticles: a review. Frontiers in Plant Science, 5, 1-11.
Huang, M., Cai, D. D., Liu, Y. H., Sun, J., Wang, J. J., Qin, C. X., . . . Kazuo, Y.
A
(2012). Investigation of a-PVA/s-PVA hydrogels prepared by freezing-thawing
M

method. Fibers and Polymers, 13, 955-962.

Jelic, A., Gros, M., Ginebreda, A., Cespedes-Sanchez, R., Ventura, F., Petrovic, M., &
ED

Barcelo, D. (2011). Occurrence, partition and removal of pharmaceuticals in

sewage water and sludge during wastewater treatment. Water Research, 45, 1165-
PT

1176.
Jones, O. A. H., Voulvoulis, N., & Lester, J. N. (2005). Human pharmaceuticals in
wastewater treatment processes. Critical Reviews in Environmental Science and
E

Technology, 35, 401-427.

CC

Kloster, G. A., Marcovich, N. E., & Mosiewicki, M. A. (2015). Composite films based
on chitosan and nanomagnetite. European Polymer Journal, 66, 386-396.
A

Kostich, M. S., Batt, A. L., & Lazorchak, J. M. (2014). Concentrations of prioritized

pharmaceuticals in effluents from 50 large wastewater treatment plants in the US
and implications for risk estimation. Environmental Pollution, 184, 354-359.
Kumirska, J., Czerwicka, M., Kaczynski, Z., Bychowska, A., Brzozowski, K., Thoming,
J., & Stepnowski, P. (2010). Application of spectroscopic methods for structural
analysis of chitin and chitosan. Marine Drugs, 8, 1567-1636.

31
Lagergren, & S. (1898). Zur theorie der sogenannten adsorption geloster stoffe.
Kungliga Svenska Vetenskapsakademiens. Handlingar Band 24, 39-50.
Larsson, D. G. J. (2014). Pollution from drug manufacturing: review and perspectives.
Philosophical Transactions of the Royal Society B-Biological Sciences, 369(1656).
Leal, M., Martinez-Hernandez, V., Meffe, R., Lillo, J., & de Bustamante, I. (2017).
Clinoptilolite and palygorskite as sorbents of neutral emerging organic
contaminants in treated wastewater: Sorption-desorption studies. Chemosphere,
175, 534-542.

T
Lessa, E. F., Gularte, M. S., Garcia, E. S., & Fajardo, A. R. (2017). Orange waste: A

IP
valuable carbohydrate source for the development of beads with enhanced

R
adsorption properties for cationic dyes. Carbohydrate Polymers, 157, 660-668.
Li, M. X., Cheng, S. L., & Yan, H. S. (2007). Preparation of crosslinked

SC
chitosan/poly(vinyl alcohol) blend beads with high mechanical strength. Green
Chemistry, 9, 894-898.

U
Lin, A. Y. C., Wang, X. H., & Lin, C. F. (2010). Impact of wastewaters and hospital
N
effluents on the occurrence of controlled substances in surface waters.
Chemosphere, 81, 562-570.
A
Lin, L., Jiang, W. B., & Xu, P. (2017). Comparative study on pharmaceuticals
M

adsorption in reclaimed water desalination concentrate using biochar: Impact of

salts and organic matter. Science of the Total Environment, 601, 857-864.
ED

Lin, S. L., & Blake, M. I. (1966). Determination of acetylsalicylic acid and barbiturate
combinations by differentiating nonaqueous titration. Journal of Pharmaceutical
PT

Sciences, 55(8), 781-789.

Magdy, E. E. (2011). Biotechnology of Biopolymers. Rjeka, Croatia: Intechem.
Meng, M. J., He, Z. H., Yan, L., Yan, Y. S., Sun, F. Q., Liu, Y., & Liu, S. J. (2015).
E

Fabrication of a novel cellulose acetate imprinted membrane assisted with chitosan-

CC

wrapped multi-walled carbon nanotubes for selective separation of salicylic acid

from industrial wastewater. Journal of Applied Polymer Science, 132, 42634.
A

Moussawi, R. N., & Patra, D. (2016). Modification of nanostructured ZnO surfaces with
curcumin: fluorescence-based sensing for arsenic and improving arsenic removal
by ZnO. RSC Advances, 6, 17256-17268.
Mussatto, S. I., Machado, E. M. S., Carneiro, L. M., & Teixeira, J. A. (2012). Sugars
metabolism and ethanol production by different yeast strains from coffee industry
wastes hydrolysates. Applied Energy, 92, 763-768.

32
Myers, A. L. (2002). Thermodynamics of adsorption in porous materials. Aiche Journal,
48, 145-160.
Ngah, W. S. W., Teong, L. C., & Hanafiah, M. (2011). Adsorption of dyes and heavy
metal ions by chitosan composites: A review. Carbohydrate Polymers, 83, 1446-
1456.
Poletto, M., Dettenborn, J., Pistor, V., Zeni, M., & Zattera, A. J. (2010). Materials
produced from plant biomass. part i: evaluation of thermal stability and pyrolysis of
wood. Materials Research-Ibero-American Journal of Materials, 13, 375-379.

T
Radjenovic, J., Petrovic, M., & Barcelo, D. (2007). Analysis of pharmaceuticals in

IP
wastewater and removal using a membrane bioreactor. Analytical and Bioanalytical

R
Chemistry, 387, 1365-1377.
Reis, N., Franca, A. S., & Oliveira, L. S. (2013). Discrimination between roasted coffee,

SC
roasted corn and coffee husks by Diffuse Reflectance Infrared Fourier Transform
Spectroscopy. Lwt-Food Science and Technology, 50, 715-722.

U
Rinaudo, M. (2008). Main properties and current applications of some polysaccharides
N
as biomaterials. Polymer International, 57, 397-430.
Rivera, W., Velasco, X., Galvez, C., Rincon, C., Rosales, A., & Arango, P. (2011).
A
Effect of the roasting process on glass transition and phase transition of Colombian
M

Arabic coffee beans. 11th International Congress on Engineering and Food

(ICEF11), 1, 385-390.
ED

Rodrigues, A. E., & Silva, C. M. (2016). What's wrong with Lagergreen pseudo first
order model for adsorption kinetics? Chemical Engineering Journal, 306, 1138-
PT

1142.
Roh, J., Umh, H. N., Yoo, C. M., Rengaraj, S., Lee, B., & Kim, Y. (2012). Waste
coffee-grounds as potential biosorbents for removal of acid dye 44 from aqueous
E

solution. Korean Journal of Chemical Engineering, 29, 903-907.

CC

Saad, M. E., Khiari, R., Elaloui, E., & Moussaoui, Y. (2014). Adsorption of anthracene
using activated carbon and Posidonia oceanica. Arabian Journal of Chemistry, 7,
A

109-113.
Saha, P., Chowdhury, S., Gupta, S., & Kumar, I. (2010). Insight into adsorption
equilibrium, kinetics and thermodynamics of Malachite Green onto clayey soil of
Indian origin. Chemical Engineering Journal, 165, 874-882.
Savjani, K. T., Gajjar, A. K., & Savjani, J. K. (2012). Drug solubility: Importance and
enhancement techniques. ISRN Pharmaceutics, 2012, 1-12.

33
Subramanyam, B., & Das, A. (2014). Linearised and non-linearised isotherm models
optimization analysis by error functions and statistical means. Journal of
Environmental Health Science and Engineering, 12, 1-6.
Teo, H. T., Siah, W. R., & Yuliati, L. (2016). Enhanced adsorption of acetylsalicylic
acid over hydrothermally synthesized iron oxide-mesoporous silica MCM-41
composites. Journal of the Taiwan Institute of Chemical Engineers, 65, 591-598.
Tripathi, S., Mehrotra, G. K., & Dutta, P. K. (2009). Physicochemical and bioactivity of
cross-linked chitosan-PVA film for food packaging applications. International

T
Journal of Biological Macromolecules, 45, 372-376.

IP
Vaz, M. G., Pereira, A. G. B., Fajardo, A. R., Azevedo, A. C. N., & Rodrigues, F. H. A.

R
(2017). Methylene Blue Adsorption on chitosan-g-poly(acrylic acid)/rice husk ash
superabsorbent composite: kinetics, equilibrium, and thermodynamics. Water Air

SC
and Soil Pollution, 228, 1-14.
Wu, F.-C., Tseng, R.-L., Huang, S.-C., & Juang, R.-S. (2009). Characteristics of

U
pseudo-second-order kinetic model for liquid-phase adsorption: A mini-review.
N
Chemical Engineering Journal, 151, 1-9.
Yan, B., Chen, Z. H., Cai, L., Chen, Z. M., Fu, J. W., & Xu, Q. (2015). Fabrication of
A
polyaniline hydrogel: Synthesis, characterization and adsorption of methylene blue.
M

Applied Surface Science, 356, 39-47.

Yang, H. G., Xu, S. B., Jiang, L., & Dan, Y. (2012). Thermal decomposition behavior
ED

of poly(vinyl alcohol) with different hydroxyl content. Journal of Macromolecular

Science Part B-Physics, 51, 464-480.
PT

Yoo, C. Y., Seong, J. S., & Park, S. N. (2016). Preparation of novel capsosome with
liposomal core by layer-by-layer self-assembly of sodium hyaluronate and chitosan.
Colloids and Surfaces B-Biointerfaces, 144, 99-107.
E

Zeng, L. X., Xie, M. J., Zhang, Q. Y., Kang, Y., Guo, X. M., Xiao, H. J., . . . Luo, J. W.
CC

(2015). Chitosan/organic rectorite composite for the magnetic uptake of methylene

blue and methyl orange. Carbohydrate Polymers, 123, 89-98.
A

Zhang, S. P., Dong, Y. Y., Yang, Z., Yang, W. B., Wu, J. Q., & Dong, C. (2016).
Adsorption of pharmaceuticals on chitosan-based magnetic composite particles
with core-brush topology. Chemical Engineering Journal, 304, 325-334.
Zheng, Y., Zhu, Y. F., & Wang, A. Q. (2014). Highly efficient and selective adsorption
of malachite green onto granular composite hydrogel. Chemical Engineering
Journal, 257, 66-73.

34
 Zhuo, N., Lan, Y. Q., Yang, W. B., Yang, Z., Li, X. M., Zhou, X., . . . Zhang, X. T.
(2017). Adsorption of three selected pharmaceuticals and personal care products
(PPCPs) onto MIL-101(Cr)/natural polymer composite beads. Separation and
Purification Technology, 177, 272-280.

Figure captions

T
Figure 1. (a) FTIR spectra and (b) XRD patterns of the starting materials, Cs/WCG0,

IP
Cs/WCG5, and Cs/WCG10.

Figure 2. (a) TGA and (b) DTG curves recorded to WCG, Cs/WCG0, Cs/WCG5, and

R
Cs/WCG10.

SC
Figure 3. Photographic and SEM images of (a,d) Cs/WCG0, (b,e) Cs/WCG5, and (c,f)
Cs/WCG10 (Mag x200, scale bar 100 μm).

U
Figure 4. Removal of pharmaceuticals from water using (a) Cs/WCG0, (b) Cs/WCG5,
N
and (c) Cs/WCG10 at different pHs values (Experimental: adsorbent dose 50 mg;
volume 250 mL; C¬0 0.5 mg/L; temperature 25 ºC; contact time 3 h; speed 100 rpm).
A

Figure 5. Adsorption kinetics of (a) MET, (b) ASA, (c) ACE, and (d) CAF on
M

Cs/WCG5 at different initial concentrations (Experimental: adsorbent dose 50 mg;

volume 250 mL; temperature 25 ºC; pH 6; speed 100 rpm).
ED

Figure 6. (a) FTIR spectra of Cs/WCG5 film and pharmaceutical-loaded Cs/WCG5

films and (b) reusability of Cs/WCG5 in consecutive adsorption/desorption cycles.
E PT
CC
A

35

View publication stats